Substituted o-carbamylhydroxamate insecticides

ABSTRACT

SUBSTITUTED O-CARBAMYLHYDROXAMATES SUCH AS METHYL O-(METHYLCARBAMYLTHIOLACETOHYDROXAMATE ARE USEFUL IN CONTROLLING INSECTS, OTHER ARTHROPOD PESTS AND PESTIFEROUS MOLLUSKS.

United States Patent Int. Cl. A01u 9/12, 9/20 U.S. Cl. 424--327 4 ClaimsABSTRACT OF THE DISCLOSURE Substituted O-carbamylhydroxamates such asmethyl O-(methylcarbamylthiolacetohydroxamate are useful in controllinginsects, other arthropod pests and pestiferous mollusks.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a divisionof my copending application Ser. No. 32,410, filed Apr. 2, 1970, nowU.S. Pat. No. 3,639,633, which in turn is a continuation-inpart of myapplication Ser. No. 670,494, filed Aug. 31, 1967, now U.S. Pat.3,576,834, which in turn was a continuation-in-part of my then copendingapplication Ser. No. 602,134, filed Dec. 16, 1966, now abandoned, whichin turn was a continuation-in-part of my then copending application Ser.No. 361,277, filed Apr. 20, 1964, now abandoned.

BACKGROUND OF THE INVENTION This invention relates tocarbamylhydroxamates and more particularly is directed to substitutedO-carbamylhydroxamates and their use in controlling insects, otherarthropod pests, and pestiferous mollusks.

Such pests as insects, ticks, mites, snails and slugs are a constantirritation and threat to man. They injure and destroy plants, consumestored food supplies, damage useful organic materials such as Wood andwool, directly set upon man and animals and invade their dwellingscontributing to the spread of some serious harmful diseases. A majorfactor in the control of such pest organisms is the chemical pesticide.There is a continuing need for new chemical pesticides to replace thoseto which pest organisms have become resistant. There is also always aneed for chemicals possessing greater activity or which are activeagainst a broader variety of pests. And, of course, there is always aneed for lower cost pesticides.

Various oximes and aldoximes are known in the art to possess biologicalactivity. Such compounds as those of U.S. Pat. No. 3,063,823, forexample, are disclosed to be herbicides, the compounds of U.S. Pat. No.3,193,- 561 are disclosed to be effective insecticides, and thecompounds of U.S. Pat. No. 3,217,037 are disclosed to be insecticides,miticides and nematocides. However, I have discovered a new class ofcarbamylhydroxamates which possess an exceptional combination ofpesticidal properties.

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SUMMARY OF THE INVENTION This invention concerns compounds of theformula wherein R is alkyl of 1 through 5 carbon atoms; haloalkyl of 1through 5 carbon atoms, containing 1 to 5 chlorine atoms, 1 to 5 bromineatoms or 1 to 11 fluoirne atoms; alkoxyalkyl of 2 through 5 carbonatoms; carboalkoxyalkyl of 3 through 6 carbon atoms; carboalkoxy of 2through 6 carbon atoms; alkylt'hioalkyl of 2 through 5 carbon atoms;cycloalkyl of 3 through 5 can-bon atoms; naphthyl; and

where X is hydrogen, fluorine, chlorine, bromine, nitro,

cyano, trifluoromethyl and dimethylamino;

Y is hydrogen, chlorine, alkyl of 1 through 4 carbon atoms, and alkoxyof 1 through 4 carbon atoms; and

Z is hydrogen, or chlorine, with the limitation that Z is chlorine onlywhen X and Y are chlorine;

R is hydrogen or methyl;

R is hydrogen or methyl;

R is alkyl of 1 through 6 carbon atoms, henzyl and chlorobenzyl; and

Q is oxygen or sulfur;

and the use of these compounds in controlling pests such as insects,ticks and mites.

The above compounds in addition to being effective pest control agentsdemonstrate a good level of safety to seeds, fruit, foliage and otherplant parts. They do not exhibit cumulative toxicity to mammals nor arethey serious eye irritants. They are not readily absorbed through theskin by humans and animals. The latter facts, together with their goodstability, facilitates safe handling and storage.

These compounds are readily metabolized or decomposed in soil, plantsand animals to non-toxic, low molecular weight materials such as carbondioxide. Thus, the compounds of this invention do not pose problemsarising from long term build-up of toxic residual materials in the soilor in biological systems.

DESCRIPTION OF THE PREFERRED EMBODIMENTS PreparationO-carbamylhydroxamates of Formula 1 are prepared by reacting ahydroxamate ester with sodium hydride in a suitable solvent such astetrahydrofuran, adding the resulting sodium salt to a solutionphosgene, and then reacting the chloroformate intermediate with twoequivalents of ammonia. The reaction is illustrated by the followingequations:

wherein R R and Q have the same meaning as above.

O-carbamylhydroxamates of Formula 1 can also be prepared by reacting ahydroxamate ester with an alkali metal cyanate and trifluoroacetic acidin an inert solvent such as benzene. This reaction is illustrated by thefollowing equation:

R wherein R R and Q are the same as above.

The hydroxamate ester intermediates required in the above synthesis canbe prepared through reaction of an imino ether hydrochloride withhydroxylamine using conditions described inthe literature. For example,see Ben, 29, 1149 (1896); Ber., 59, 2395 (1926); Ben, 69, 2352 (1936). Asignificantly improved method for carrying out this reaction isdisclosed in copending application Ser. No. 571,963, now U.S. Pat. No.3,374,260.

Thiolhydroxamate intermediates can also be prepared by chlorination ofan aldoxime in an inert solvent to form the corresponding hydroxamoylchloride (see Ber., 27, 2197 (1894)), followed by reaction of the latterwith the alkali metal salt of an alkyl mercaptan.

The O-(methylcarbamyl)hydroxamates of this invention are prepared bytreating a hydroxamate ester, prepared as described above, with methylisocyanate in the presence of an aprotic solvent such as benzene,toluene, methylene chloride, 1,2-dichloroethane, ethyl ether,tetrahydrofuran or their mixtures. Frequently, it is advantageous tocarry out the reaction in the presence of a small amgunt of1,4-diazabicyclo[2.2.2] octane, triethylamine, or other basic materialas a catalyst. This method is illustrated by the following equation:

R C=NOH CHaNCO R C=NO( ilNHCH Q-' l R4 wherein R R and Q have the samemeaning as above.

The O-(dimethylcarbamyl)hydroxamates of this invent1on can be preparedby reacting a hydroxamate ester with sodium hydride in a solvent such astetrahydrofuran, and then treating the resulting sodium salt withdimethylcarbamyl chloride. This method is illustrated by the followingequations:

R,G=N iN oH3)i wherein R R and Q have the same meaning as above.

Pests controlled Insects, ticks and mites that are killed, repelled,prevented from reproducing, or otherwise prevented from causing damageby the compositions of this invention are represented by, but notlimited to, the following:

Insects, ticks and mites that are killed, repelled, prevented fromreproducing, or otherwise prevented from causing damage by thecompositions of this invention are represented by, but not limited to,the following:

Aphids:

Apple aphid-Aphis pomi Bean aphidAphis fabae Cabbage aphid-Brevicorynebrassicae Corn leaf aphidRhopal0siphum maidis Corn root aphid-Arturaphismaidiradicis Cotton aphidAphis gossypii Greenbug-Schizaphis graminumGreen peach aphid-Myzus persicae Potato aphid-Macr0siphum euphorbiaeRose aphid-Macr0siphum ro ae Woolly apple aphidErios0ma lanigerumArmyworm:

ArmywormPsuedaletia unipuncta Beet armyworm-Sp0d0ptera exigua FallarmyWOrm-Laphygma frugiperda Southern armywormPr0denia eridania Beetles:

Asiatic garden beetleMaladera castanea Bean leaf beetleCer0tomatrifurcata Blister beetle-Epicauta spp. Cigarette beetleLasi0dermaserricorne Colorado potato beetleLeptinotarsa decemlineata Japanesebeetle--P0pillia japonica Mexican bean beetleEpilachna varivestis Squashbeetle-Epilachna boreali Sugarcane beetle-Euethe0la rugicepsWhite-fringed beetleGraph0gnathus leucoloma Boll weevil-Anthonomusgrandis Bollowrm--Heliothis zea Borers:

European cornborer-Ostrinia nubilalis Peach tree borer-Sanninoideaexitiosa Squash vine borer-Melittia cucurbitae Sugarcane borer-Diatraeasaccharalis Rice borers-Chilo spp. Butterflies:

Clouded sulfurC0lias philodice Imported cabbagewormPieris rapaeCaterpillars:

Alfalfa caterpillar-Calms eurytheme Eastern tent caterpillar-Malacosomaamericanum Forest tent caterpillarMalac0soma disstria CornearwormMeli0this Zea (see bollworm Cotton leaf perforatorBucculatrixthurberiella Cotton stainer-Dysdercus suturellus Flea beetles:

Corn flea beetle'Chaetocnema pulz'caria Potato flea beetleEpitrixcucumeris Tobacco flea beetleEpitrix hirtipennis Fleahopper,cottonPsallus serz'atus Flies:

Hessian fly-Mayetiola destructor Horn fly-Haemat0bia irritans HouseflyMu ca domestica Stable flyStom0xys calcz'trans Fruit flies:

Mediterranian fruit fiy-Ceratitis capitata Mexican fruit fly-A nastrephaludens Oriental fruit flyDacus dorsalis German cockroach-Blattellagermanica GrasshopersMelanoplus spp., Camnula spp. Leaf rollers:

Fruit tree leaf rollerArchips argyrospilus Red-banded leafrollerArgyr0taenia velutinana Leafhoppers:

Beet leafhopper-Circulifer tenellus Potato leafhopperEmp0asca fabaeSugarcane leafhopper-Perkinsiella saccharicz'da Leafworm, cotto11Alabamaargillacea Loopers:

Alfalfa looperAutographa californica Cabbage looper-Trich0plusia niMaggot, seed-corn-Hylemya platura Mealybugs:

Citrus mealybug-Plannococcus citri Pineapple mealybugDysmicoccusbrevipes Mites:

Citrus red mite--Panonychus citri Clover mite-Bryobia praetz'osaEuropean red mite-Panonychus ulmi Pacific spider mite-Tetranychuspacificus Two-spotted spider mite-Tetranychus urticae Mosquitoes Commonmalaria mosquito-Anopheles quadrimaculatus Salt-marsh mosquito-A edessollz'citans Southern house mosquito-Culex pipiens quinquefasciatusMoths Black army cutworm-Actebia fennica Black cutworm--Agr0tis z'psilonCodling moth-Carpocapsa pomon ella Diamondback moth-Plutellamaculipennis European pine shoot moth-Rhyacionia buoliana Greencloverworm-Plathypena Scabra Grape berry moth-Paral0besia viteana Gypsymoth- Porthetria dispar Oriental fruit moth-Grapholitlza mlolesta Potatotuberworm-Phthorimaea operculella Spruce budW0rm-Ch0rist0neurafumiferana Tussock moth, white markedHemer0campa leucostigma Vel etbeancaterpillar-Anticarsia gemmatalis Pink bollwormPectinoph0ra gossypiellaPlum curculio-Conotrachelus nenuphar Rootworms:

Northern corn rootworm-Diabrotica longz'cornis Southern cornrootworm-Diabrotica undecimpunctaza howardi Western cornrootwormDiabr0tica virgifera Slugs:

Gray field slug-Der0ceras laeve Gray garden slugDeroceras reticulatumSpotted garden slug-Limax maximus Stink bugs:

Brown stink bug-Euschz'stus servus Green stink bug-Acrosternum hilareThrips Onion thrips-Thrips tabaci Tobacco thrips-Frankliniella fuscaTicks American dog tick-Dermacentor variabilis Fowl tick-Argus persicusTobacco budwormHeliothis virescens Tobacco hornworm-Manduca sexta Tomatohornworm-Manduca quinquemaculata Weevils Alfalfa weevil-Hypera posticaGranary weevil-Sitophilus granarius Rice weevil: Sitophilus oryzaeSweet-potato weevil-Cylas formicarius elegantulus Whiteflies:

Citrus black fly-Aleurocanthus woglumi Citrus white fly-Dialeurodescitri.

Preferred compounds Compounds of Formula 1 which are preferred becauseof their high order of pesticidal activity are those of the formula R isthe same as in Formula 1; R is alkyl of 1 through 3 carbon atoms; and Ris alkyl of 1 through 3 carbon atoms.

Particularly preferred compounds of Formula 1 because of theireffectiveness against specific insects are:

Methyl O (methylcarbamyl)thiolacetohydroxamate-- highly effectiveagainst housefly, aphids, mites, southern armyworm, and boll weevil; and

Methyl O carbamylthiolacetohydroxamate-highly effective againsthousefly, aphids and boll Weevile.

Other particularly preferred compounds are:

Formulations Compositions of this invention suitable for practical useas pesticides will include one or more compounds of Formula 1 aboveeither individually, as a complex, in ad mixture with each other, or inadmixture with other pesticides and agricultural adjuvants such asresins, surfaceactive agents, solid or liquid diluents and othermaterials as desired to produce wettable powders, suspensions,emulsifiable concentrates, dusts, solutions, granules, pellets orhigh-strength compositions.

The surface-active agents or surfactants, as they are sometimes called,useful in the formulations of this invention act as Wetting, dispersingand emulsifying agents which assist dispersion of the active material ina spray. Additionally, the surfactants act as spreaders which aid inobtaining even coverage of the surfaces to be protected from insects andother pests. The surfactants can include such anionic, non-ionic andcationic agents as have been used heretofore in pesticidal compositionsof similar type. A detailed list of such agents may be found inDetergents and Emulsifiers Annual (John W. Mc- Cutcheon, Inc.).

Anionic and non-ionic surfactants are preferred. Among the anionicsurfactants, preferred ones are alkali and alkaline earth salts ofalkylarylsulfom'c acids, such as dodecylbenzenesulfonates andalkylnaphthalenesulfonates, dialkyl sodium sulfosuccinate esters, sodiumlauryl sulfate, sodium N-methyl-N-oleoyltaurate, sodium dodecyldiphenylether disulfonate and the oleic acid ester of sodium isethionate. Amongthe non-ionic surfactants, preferred ones include octylphenylpolyethylene glycol ethers, dodecylphenyl polyethylene glycol ethers,polyoxyethylene derivatives of sorbitan fatty esters and long-chainalcohols and mercaptans, as well as polyoxyethylene esters of fattyacids.

Preferred dipsersants are alkali and alkaline earth salts oflignosulfonic acids, salts of polymerized alkylarylsulfonates which aresold under the "Daxad and Darvan trademarks, as well as methylcellulose,polyvinyl alcohol and the like.

Surfactants can be used in compositions of this invention in amounts ofup to 50% by weight based on the total weight of the resultinginsecticidal composition.

The compositions can contain, with or without a surfactant, one or morefinely divided solid diluents such as natural silicates, e.g., talc,sepiolite, pyrophyllite; clays, e.g., montmorillonite, kaolinite,attapulgite, diatomaceous earth, synthetic magnesium silicate, syntheticfine silicas, calcium silicate, calcium sulfate, calcium carbonate,calcium phosphate, powdered charcoal and flours derived from naturalsources such as walnut shell, redwood, cottonseed and the like. Thefinely divided solids can be used in the compositions of this inventionat a concentration of 1 to 98% by weight based on the total weight ofthe resulting pesticidal composition. Preferred finely divided solidformulations are high-strength compositions and powders containing 1 to25% of synthetic fine silica and 75 to 99% active ingredients; wettablepowders containing 5 to 75% active ingredients, 0.5 to 50% surfactants,remainder finely divided solid diluents; dusts containing from 1 to 20%active ingredients; and dust concentrates containing to 80% activeingredients.

Organic liquids which are suitable for the preparation of solutions,suspensions and emulsifiable concentrates of the compounds of thisinvention include alcohols, glycols, Cellosolves, Carbitols, ketones,esters, sulfoxides, amides, parafiinic hydrocarbons, aromatichydrocarbons, and halogenated hydrocarbons. Solvent combinations inwhich water miscible solvents are combined with water, are particularlyuseful. Ordinarily, solvent choice is dictated by the solubility of theactive compound to be used and whether a suspension or solution isdesired. With both polar and non-polar organic solvents, butparticularly the latter, inclusion of 0.2 to 2.0 parts, per part ofcarbamate insecticide, of a phenolic compound containing at least onephenolic hydroxy group per molecule, functions to increase thesolubility of some of the compounds of this invention such asmethyl-O-(methylcarbamyl)thiolacetohydroxamate, ethyl O(methylcarbamyl)thiolacetohydroxamate, and methylO-(dimehtylcarbamyl)-thiolacetohydroxamate. Such inclusion also improvesthe compatibility of these compounds with other insecticides such asEPN, methoxychlor or DDT, which are soluble in nonpolar solvents.Representative of such phenolic compounds are the cresols,o-t-butylphenol,a-naphthol, resorcinol and bisphenol A.

Preferred solutions are those containing 20 to 50% active ingredient and50 to 80% solvent or solvent-phenolic compound combination. Preferredsolvents are ethylene glycol methanol, methylene chloridedimehylformamide,

Cellosolve, aqueous mixtures of these solvents, xylene,

heavy aromatic naphtha, isophorone and combinations of any of these.Suspension formulations are generally preferred if the solubility of theactive ingredient or active ingredients in the liquid carrier is lessthan about 0.1 percent.

For aerosol formulations low-boiling halognated hydrocarbons arepreferred as solvents and propellants, although they can be partiallyreplaced by low-boiling hydrocarbons which act as propellants. Aerosolformulations ordinarily contain an organic or aqueous liquid in therange of 20 to 98% by weight based on the total weight of the pesticidalcomposition.

Formulations in the form of granules and pellets are physically stable,particulate compositions containing a compound of Formula 1 whichadheres to or is distributed through a basic matrix of a coherent, inertcarrier with macroscopic dimensions. In order to aid leaching of theactive ingredient from the granule or pellet, a surfactant can bepresent.

Suitable carriers are preferably of mineral origin such as naturalclays, some pyrophyllites, and vermiculite. Other carriers can be oforgnaic origin, such as granular corn corbs or charcoal. Suitablesurfactants are anionic or non-ionic.

For the granule compositions of this invention, most suitable carriersare of two types. The first are porous, absorptive, preformed granules,such as preformed and screened granular attapulgite, granular corncorbs, granulated charcoal, or heat-expanded, granular, screenedvermiculite. On such preformed granules, a solution of the active agentcan be sprayed and will be absorbed at concentrations up to 25 weightpercent of the total weight. The active agent is preferably applied in awater solution when its solubility permits. In some instances, it ispreferred to use hot rather than cold water to obtain a moreconcentrated spray solution. In other instances, an organic solvent ormixed organic-aqueous solvent is preferable to obtain increasedsolubility of the active ingredient. Ordinarily, if an organic solventis used it is preferably selected from among methylene chloride, methylCellosolve, dimethylformamide and the like.

Preformed granules can also be treated with a melt of active ingredientif the active ingredients melting point is sufiiciently below itsdecomposition temperature. When this means of application is used, theactive ingredient in a very finely divided form is deposited on thesurface of the granules such as by tumbling in a mixer. The finelydivided active agent can if desired contain minor amounts of diluentssuch as synthetic silicas, natural clays and surface-active agents.After the active agent is distributed on the granules the granules areheated to above the melting point of the active agent preferably whiletumbling is continued. The granules are then cooled and contain activeingredient within as well as fixed on their surfaces.

The second type of carrier suitable for granules as well as pellets isinitially in a powder form. Powdered kaolin clays, hydrated attapulgiteor bentonite clays such as sodium, calcium and magnesium bentonite, orpowdered charcoal are blended with the active ingredient and themixtures are then granulated or pelleted. Water-soluble salts can beincluded in the compositions to aid in disintegration of the granulesand pellets in the presence of moisture. Such granules or pellets can bemade containing 25 to 30 weight percent of active ingredient, but morefrequently a concentration of 5 to 10 percent is preferred for optimumdistribution. Such granular compositions are most useful in a size rangeof 15 to mesh (U.S.S.), i.e., 0.25 to 1.4 millimeters.

The most preferred formulation for granules or pellets is 2 to 20 Weightpercent active ingredient, 0 to 5 weight percent surfactant and to 98percent inert mineral carrier.

Sprayable granules can also be prepared. These are small solid particlescontaining 2 to percent active ingredient. The particles can be appliedsuch as by suspending them in a liquid and spraying the suspensionthrough a suitable nozzle.

Additional modifiers can be used to advantage in the compositions ofthis invention. Thus, although the compounds of Formula 1 are quitestable under most conditions, the use of a desiccant, buffering agent ormaterials such as urea, which inactivate catalytic sites on diluentparticles can prove desirable. Additives which will inhibit corrosion,reduce foam, reduce caking and increase flocculation can also be used.In addition, bactericides, fungicides, bacteriostats and fungistats andother insecticides are often desirably present in the compositions ofthis invention in amounts of 0.025 to 10 parts by weight for each 1 partby weight of compound of Formula 1. Suitable biologically activecompounds are mentioned below.

The compositions of this invention can be prepared by methods generallyused for pesticidal compositions of similar type. The solidcompositions, with the exception of granules and pellets are prepared ina blending operation where the active ingredients are either dryblendedwith the diluents or impregnated by spraying a solution on a tumblingdiluent mass. After blending the process will usually include passagethrough a grinder such as an attrition mill, a hammer mill or a fluidenergy mill.

Solutions are prepared by stirring the combined ingredients; in somecases warming may speed solution and in others cooling or pressure maybe required to prevent evaporation of the solvent. Aqueous and oilsuspensions are prepared by mixing the insoluble active ingredient andother ingredients and ball-milling or sand-grinding the mixture toproduce a concentrated slurry of very finely divided particles.

Combinations As mentioned above, in many instances, it is advantageousto combine the compounds of Formula 1 with each other and with otherpesticides. Such combinations can be made by the user at the time ofapplication or prepared by a manufacturer as a ready-to-use formulationin one of the manners described above.

Among the advantages of combinations are control of pests with a smallertotal amount of chemical; control of pairs of communities of pests andpathogens; and regulation of the degree of residual eifect. All of theseadvantages can be accomplished merely by selecting chemicals forcombination which complement one another in activity.

Ordinarily the chemicals combined will be used at from 0.1 to 3 timestheir normal use rate. However, rates are clearly dependent upon thespecific chemicals combined, their intended use, and other obviouscriteria.

Pesticides which can advantageously be combined with the compounds ofFormula 1 include, but are not limited to, the following:

1,2,3,4,l0,10 hexachloro-1,4,4a,5,8,8a hexahydro-1,4-

endoexo-S,B-dimethanonaphthalene (aldrin);

1,2,3,4,5,fi-hexachlorocycylohexane (lindane);

1,2,3,4,5,6,7,8,8-octachloro-2,3,3a,4,7,7a hexhydro 4,7-

methanoindene (chlordane);

1,1,l-trichloro-2,2-bis(p-chlorophenyDethane (DDT);

1,2,3,4,10,10-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8aoctahydro-1,4-endoexo-5,8-dimethanonaphthalene(dieldrin);

l,2,3,4,10,10-heXachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a-

octahydro-1,4-endoe11do-4,6-dimethanonaphthalene (endrin);

6,7,8,9,10,lO-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9

methano-2,4,3-benzodioxathiepin 3-oxide (Thiodan);

l-(or 3a),4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methanoindene;

1,1, l-trichloro-2,2-bis(p-methoxyphenyl) ethane (methoxychlor);

l,1-dichloro-2,2-bis(p-chlorophenyl)ethane (TEDE);

chlorinated camphene having a chlorine content of 67- 69% (toxaphene);

chlorinated terpenes having a chlorine content of ca.

66% (Strobane);

2-nitro-1,1-bis(p-chlorophenyl) butane;

l-naphthyl N-methylcarbamate (carbaryl);

methylcarbamic acid, ester with 4-(dimethylamino)-3,5-

dimethylphenol;

methylcarbamic acid, ester with 1,3-dithiolan-2-one oxime;

methyl N-methylthiolcarbamate;

methyl methylthiolcarbamate;

0,0-diethyl O-[2-isopropyl-4-methylpyrimid-6-yl] thiophosphate(diazinon);

0,0-dimethyl 1-hydroxy-2,2,2-trichloroethyl phosphonate;

0,0-dimethyl S-(1,2-dicarbethoxyethyl) dithiophosphate (malathion);

0,0-dimethyl O-p-nitrophenyl thiophosphate (methyl parathion);

0,0-diethyl O-p-nitrophenyl thiophosphate (parathion);

0,0-dimethyl O-(3-chloro-4-nitrophenyl) thiophosphate;

dl-2-cyclopentenyli-hydroxy-3-methyl-2-eyclopenten-lone;

dl-chrysanthemumate;

0,0-dimethyl 0-(2,2-dichlorovinyl) phosphate (DDVF);

mixture containing 53.3% Bulan, 26.7% Prolan and 20.0% relatedcompounds;

0,0-dimethyl O-(2,4,5-trichlorophenyl) phosphorothioate;

0,0-dimethyl S-(4-oxo-1,2,3-benzotriazine-3 (4H) -ylmethyl)phosphorodithioate (Guthion);

bis-(dimethylamino)phosphonous anhydride;

dimethyl phosphte of 3-hydroxy-N-methyl-cis-crotonamide (Azodrin);

0,0-diethyl O-(2-keto-4-methyl-7-rt-pyranyl)thiophosphate;

0,0-diethyl (S-ethylmercaptomethyl) dithiophosphate (phorate);

calcium arsenate;

sodium aluminofluoride;

dibasic lead arsenate;

2-chloroethyl 1-methyl-2- (p-terL-butylphenoxy)ethyl sulfite;

azobenzene;

ethyl 2-hydroxy-2,2-bis(4-chlorophenyl)acetate;

0,0-diethyl O-[2-(ethylmercapto)ethyl] thiophosphate;

2,4-dinitro-6-sec-butylphenol;

O-ethyl O-p-nitrophenyl benzenethiophosphonate (EPN);

4-chlorophenyl 4-chlorobenzenesulf onate;

p-chlorophenyl phenyl sulfone;

tetraethyl pyrophosphate;

1, l-bis- (p-chlorophenyl ethanol;

1,1-bis-(p-chlorophenyl)-2,2,2-trichloroethanol (Kelthane);

p-chlorophenyl p-chlorobenzyl sulfide;

bis-(p-chlorophenoxy)methane;

3-( l-methyl-Z-pyrrolidyl) pyridine;

mixed esters of pyrethrolone and cinerolone keto-alcohols and twochrysanthemum acids;

cube and derris, both whole root and powdered;

ryanodine;

mixture of alkaloids known as veratrine;

dl-2-ally1-4-hydroxy-3-methyl-2-cyclopenten-l-one esterified with amixture of cis and trans dl-chrysanthemum monocarboxylic acids;

butoxypolypropylene glycol;

p-dichlorobenzene;

2-butoxy-2'-thiocyanodiethyl ether;

naphthalene;

1, 1-dichloro-2,2-bis (p-ethylphenyl) ethane;

p-dimethylaminobenzenediazo sodium sulfonate;

quinone oxyaminobenzooxohydrazone;

tetramethylthiuram monosulfide;

tetramethylthiuram disulfide (triram);

metal salts of ethylenebisdithiocarbamic acid, e.g., manganese, zinc,iron and sodium salts;

pentachloronitrobenzene;

2,3-dihydro-5-carboxyanilido-G-methyl-1,4-oxathiin;

n-dodecylguanidine acetate (dodine);

N-trichloromethylthiotetrahydrophthalimide (captan);

phenylmercury acetate;

2,4-dichloro-6- (o-chloroanilino) -s-triazine (Dyrene);

N-methylmercury-p-toluenesulfonanilide;

chlorophenolmercury hydroxides;

nitrophenolmercury hydroxides;

ethylmercury acetate;

ethylmercury 2,3-dihydroxypropylmercaptide;

methylmercury acetate;

methylmercury 2,3-dihydroxypropylmercaptide (Ceresan L);

3,3-ethylenebis(tetrahydro-4,6-dimethyl-2H-1,3,5-

thiadiazine-Z-thione) (Cylan);

methylmercury dicyandiamide;

N-ethylmercury p-toluenesulfonanilide;

1,4-dichloro-2,5-dimethoxybenzene (chloroneb) metal (e.g., iron, sodiumand zinc) ammonium and amine salts of dialkyldithiocarbamic acids;

tetrachloronitroanisole;

hexachlorobenzene;

hexachlorophene;

methylmercury nitrile;

tetrachloroquinone;

N-trichloromethylthiophthalimide;

-ethoxy-3-trichloromethyl-1,2,4-thiadiazole;

1,2-dibromo-3-chloropropene;

dichloropropane-dichloropropene mixture;

ethylene dibromide;

1-chloro-2-nitropropane;

chloropicrin;

sodium dimethyldithiocarbamate;

tetrachloroisophthalonitrile;

1-(n-butylcarbamoyl)-2-benzimidazolecarbamic acid methyl ester;

streptomycin;

2-(2,4,5-trichlorophenoxy)propionic acid;

p-chlorophenoxyacetic acid;

l-naphthaleneacetamide; and

N-l-naphthylacetamide.

Of the above compounds, those which are insecticides and with whichcompounds of Formula 1 are preferably combined include DDT; TDE; EPN;Azodrin; toxaphene; Strobane and Thiodan.

Fungicides and fungistats of the above list with which pounds of Formula1 are preferably combined include PCNB; thiram; dodine; maneb;methylmercury 2,3dihydroxypropylmercaptide; methylmercury acetate;N-ethylmercury p-toluenesulfonanilide; 1,4-dichloro 2,5dimethoxybenzene; l-(n-butylcarbamoyl) 2 benzimidazolecarbamic acid,methylester; N-trichloromethylthiotetrahydrophthalimide;N-trichloromethylthiophthalimide; sodium and calcium propionate; and3,3'-ethylenebis(tetrahydro-4,6-dimethyl)-2H-1,3,S-thiadiazine-Z-thione.

Bacteriostats and bacteriocides of the above list with which compoundsof Formula 1 are preferably combined include tribasic copper sulfate andstreptomycin sulfate.

Specific combinations which are preferred and their area of exceptionalutility include:

(a) Methyl O-(methylcarbamyl)thiolacetohydroxamate and methylO-carbamylthiolacetohydroxamate in ratios ranging from 1:4 to 4:1 foruse on cotton plants.

(b) Methyl O-(methylcarbamyl)thiolacetohydroxamate and1,4-dich1oro-2,S-dimethoxybenzene (chloroneb) in ratios ranging from 1:6to 6:1 for use on cotton seed. The chloroneb can be replaced in thiscombination by one of the following compounds, their mixtures with eachother or their mixtures with chloroneb; pentachloronitrobenzene, captan;tetramethylthiuram disulfide; l-chloro-Z- nitropropane; S-ethoxy 3trichloromethyl-l,2,4-thiadiazole; and p-dimethylaminobenzene-diazosodium sulfonate. Such combinations are useful on seeds other thancotton including both vegetable and agronomic crops.

(c) Methyl O-(methylcarbamyl)thiolacetohydroxamate, chloroneb, andl-(n-butylcarbamoyl) 2 benzimidazolecarbamic acid, methyl ester, inratios ranging from 1:4:4 to 4:1:1, for use on cotton seed and othercrop seed.

(d) Methyl O-carbamylthiolacetohydroxamate and DDT, in ratios rangingfrom 1:6 to 6:1 for use on cotton plants. In other combinations for thisuse, the DDT can be replaced by one of the following compounds, theirmixtures with each other and their mixtures with DDT: endrin, carbaryl;malathion, methyl parathion; Guthion and toxaphene.

(e) Methyl 0-(methylcarbamyl)thiolacetohydroxamate andl-(n-butylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester, inratios ranging from 1:3 to 3:1, for use on rice plants in seed-bed,paddy or field for the control of insects and disease.

(f) Ethyl O-carbamylthiolacetohydroxamate combined with EPN, carbaryl,Guthion, malathion, methyl parathion or parathion in ratios ranging from1:4 to 4:1 for use on rice plants.

(g) Methyl O-carbamylthiolacetohydroxamate combined with DDT endrin EPNtoxaphene malathion parathion Guthion carbaryl or methoxychlor in ratiosranging from 1:5 to 5 :1 for use on potato plants. The methylO-carbamylthiolacetohydroxarnate can be replaced in this combination byother compounds of Formula 1 such as methylO-carbamylthiolpropionohydroxamate.

(h) Methyl O (methylcarbamyl)thiolacetohydroxamate combined withparathion, aldrin, diazinon or phorate, in ratios ranging from 1:3 to 3:1 for application to soil prior to or during the planting of corn. Themethyl O-(methylcarbamyl)thiolacetohydroxamate can be replaced in thiscombination by other compounds of Formula 1 such as ethylO-(methylcarbamyl)thiolacetohydroxamate.

(1) Methyl O (methylcarbamyl)thiolacetohydroxamate combined with DDT,methoxychlor, malathion, parathion, lead arsenate, Guthion, carbaryl ordieldrin in ratios ranging from 1:4 to 4:1, for use on apples and othercrops.

(j) 0 carbamylthiolacetohydroxamate combined with DDT, carbaryl, EPN,toxaphene, methoxychlor or diazinon, in ratios ranging from 1:5 to 5:1for use on corn plants.

(k) Methyl O carbamylthiolpropionohydroxamate combined with TDE, DDT,Guthion, malathion, diazinon, parathion or carbaryl, in ratios rangingfrom 1:6 to 6: 1, for use on tobacco plants in seed-bed or field. Themethyl O-carbamylthiol propionohydroxamate can be replaced in thiscombination by other compounds of Formula 1 such as methyl or ethylO-(methylcarbamyl)-thiolpropionohydroxamate.

(l) Ethyl O carbamylthiolacetohydroxamate and chlordane, in ratiosranging from 1:8 to 8:1, for use on sugarcane seed pieces in the furrowat the time of plantmg.

(m) Methyl O (methylcarbamyl)thiolacetohyroxamate combined withtoxaphene, carbaryl, endrin or Guthion, in ratios ranging from 1:12 to12:1, for use on surgarcane foliage.

(n Methyl O carbamylthiolacetohydroxamate combined with methoxychlor,carbaryl, malathion, DDT or toxaphene, in ratios ranging from 1:4 to4:1, for use on shade trees or forest lands.

(0) Methyl O (methylcarbamyl)thiolacetohydroxamate combined withchlordane, DDT, diazinon or parathion, in ratios ranging from 1:5 to 5:1, for use in soil prior to or during planting of potatoes.

(p) Methyl O (methylcarbamyl)thiolacetohydroxamate plus Guthion,diazinon, malathion, parathion, methoxychlor, DDT, or toxaphene, inratios ranging from 1:5 to 5: 1, for use on cabbage or other cruciferouscrops.

Complexes The compounds of Formula 1 form crystalline complexes withcompounds such as urea, thiourea, and dicyandiamide, hereinafterreferred to as complexing agents, in 1:1 molar ratios. Such complexescan be prepared read ily by dissolving equal molar proportions of acompound of Formula 1 and a complexing agent in a mutual solvent such asmethanol and then allowing the solvent to evaporate.

The complexes thus formed are ordinarily crystalline solids having sharpmelting points. The solubility of the complex in many solvents Willordinarily differ from the parent compounds. These properties make thecomplexes particularly useful for isolating a compound of Formula 1 fromits reaction mixture. They also make the complexes particularly suitedfor use in many formulations. Thus, for example, in the preparation ofsolutions, high-strength compositions and wettable powders complexes canbe of particular advantage and in any of the compositions of this 13invention the complexes are ordinarily as suitable for use as, andshould be regarded as the equivalent of, the compound of Formula 1.

Application In applying the compounds of this invention for pestcontrol, the compound, of course, is applied in an amount sufficient toexert the desired pesticidal action. The amounts required, however, togive pesticidal action are governed by such variables as temperature,time of the year, moisture, type of application, pests to be controlled,crop being treated and the like.

Compounds are applied to the locus or area to be protected. Theapplication can be made directly upon the locus or area to be protectedfrom pests during the period of infestation. Alternatively, theapplication can be made in advance of an anticipated infestation so thatthe pests will ingest or contact the active compound and be killed.

More particularly the compounds of Formula 1 can be used to controlinsects and mites attacking living plants, by redistributing thecompound over those plant surfaces already infested or subject tosubsequent attack by these pests. Use rates for this type of applicationare in the range of 0.05 to 30 pounds of active ingredient per acre.More preferred rates are in the range of 0.1 to 15 pounds per acre andthe most preferred rates in the range of 0.2- 7 lbs. per acre.Applications such as these may need to be repeated one or more times atintervals of 3 to 20 days. Such applications are made with any of avariety of widely available types of equipment regularly used to applypesticides to plants. In addition to conventional spray applications,the compounds of Formula 1 can be applied by ultra low volumeapplication as concentrated solutions, used undiluted, at rates of from1 pint to 2 gallons of total spray per acre. Conventional aerial sprayswill ordinarily utilize diluted solutions at rates of from 2 to 20gallons per acre. Mist blower sprays, utilizing diluted solutions, willordinarily be made at rates of from 2 to 600 gallons per acre andpreferably at rates of from 20 to 200 gallons per acre. To facilitateapplications of this nature, the compounds of this invention can beformulated to improve handleability or efficacy as described previously.

Other effective methods of application include:

(a) Application to a part, such as the stem, of some plants, such ascotton, after which the chemical is systemically moved throughout theplant such that the entire plant is protected.

(b) Application to the seed of agricultural, horticultural andornamental crops to protect the seed during storage and shipping priorto planting as well as to protect the seed and seedlings (as a result ofsystemic move ment) from attack by insects and mites after planting. Thepreferred rates for application to seed are in the range of- .01 to 30ounces of the active compound of this invention per 100 pounds of seed.The most preferred rates are in the range of 1 to 10 ounces per 100pounds of seed.

(c) Application to soil in which plants are to be planted or are growingto protect seed and plants from attack by insects and mites. Suchprotection is against both soil insects attacking the roots and insectsand mites attacking the above-ground parts of the plants. Preferred userates are in the range of 0.1 to 50 pounds of active ingredient per acreof area actually treated. The most preferred rates are in the range of0.25 to 20 pounds per acre. Such application includes placing thepesticidal composition in the furrow at the time of planting; mixing thecomposition into the soil at or after planting; and depositing thecomposition on the surface of the soil after planting so that it iscarried down into the soil by rainfall or irrigation. Granularformulations are particularly useful in this type of applicationalthough other formulations can be used effectively.

((1) Application to the walls and floors of structures to controlinsects, ticks and mites. Such applications to 14 be repeated as needed.Preferred use rates for such applications are in the range of .001 to 2pounds of active ingredients per 1,000 square feet of surface treated.The most preferred rates are in the range of .01 to 0.4 pound of activeper 1,000 square feet of surface.

(e) Application to animals to control insects, ticks and mites causinginjury or annoyance, or dissemination of disease. The compound of thisinvention to be applied to the animals to be protected by sprays, dustsor dips in such a way as to give a more or less uniform coating. Suchapplications to be repeated as needed.

(f) To land areas (including marsh or swamp) for the control of insects,ticks or mites causing injur or annoyance or disseminating disease tohumans or animals. Preferred use rates are in the range of .01 to 9pounds of active compound of this invention per acre 1 to 5 times ayear. The most preferred rates are in the range of .03 to 3 pounds ofactive per acre on the same schedule.

(g) Application to leaves of plants to facilitate absorption andtranslocation within the treated leaves. Application will ordinarily bemade at those rates first described above.

(h) Application to leaves of plants in such a manner so as to reduceabsorption and translocation, and increase retention on externalportions of the leaves. This increases the contact action of thecompounds of Formula 1 and their residual activity by preventingabsorption of the compounds into the plant and attendant deactivation ofthe compound by metabolism in the plant.

(i) Application in the form of baits to combat pests in areas whereconventional spraying is not practical, such as household pests, pestsliving underground, and chewing pests attacking crop areas too large tobe protected by spraying. These formulations are particularly useful forcontrolling pests in soybean, cotton and truck garden crops. Baitsordinarily will contain from 0.5 to 5 percent active ingredient and thefood portion of the bait is selected according to the tastes of thepests being treated. Baits should be spread very thinly and uniformly toavoid danger to other forms of animal life.

(j) Application at low rates to insects as knockdown agents. Manyinsects, such as the spruce budworm, when knocked out of foliage ontothe ground, are unable to get back to the host plant to continuefeeding. Application is made at rates of from 0.5 to 2 ounces per acreand thus reduces both the cost of treatment and the amount of chemicalreleased into the biosphere.

In the applications enumerated above (a) through (f)) the distributionof the compounds of this invention may be simplified and made moreaccurate through the use of the formulations and compositionsdescribed'herein.

The following examples illustrate the invention. References to parts orpercentages are by weight unless otherwise specified. The compoundsreferred to in the examples as well as those referred to above andrepresented by Formulae 1 and 2 can exist as synand anti-isomers or asmixtures of these isomers.

EXAMPLE 1 To a slowly stirred mixture of 10.5 parts of methylthiolacetohydroxamate, 50 parts of benzene and 13 parts of sodiumcyanate, is added 15 parts of trifiuoroacetic acid. The temperaturerises to 32 C. and is held there by external cooling. After addition of50 parts of methylene chloride, the mixture is stirred for severalhours, and then treated with 25 parts of water. A small amount ofinsoluble material is filtered off. The two phases of the filtrate areseparated and the aqueous phase is reextracted with methylene chloride.Evaporation of the combined organic phases gives 5 parts of an oilysolid which is recrystallized from isopropanol to yield 3.7 parts ofmethyl O-carbamylthiolacetohydroxamate.

The methyl O-carbamylthiolacetohydroxamate is formulated and applied asfollows:

Percent Methyl O-carbamylthiolacetohydroxamate 5.0 Sodium dioctylsulfosuccinate 0.5 Polymerized alkylarylsulfonates 1.0 Pyrophyllite 68.5Attapulgite clay 25.0

be formulated and applied in like manner.

EXAMPLE 2 Percent Methyl O-carbamylthiolacetohydroxamate 95.0 Syntheticsilica 5.0

The above high strength composition is prepared by coarse grinding andscreening through a screen having 16 meshes/cm.

This composition is added to water in an amount to provide 0.25 pound ofthe active ingredient per 100 gallons. After an adequate time has passedto allow the active compound to go into solution, ordinarily between 2and minutes depending upon the temperature of the water, the resultingsolution is applied as a wetting spray to cabbage plants on whichcabbage loopers (Trichoplusia ni), are feeding. All of the cabbageloopers are killed by the spray.

DDT can be added to the above spray at the rate of 1.0 pound of activeingredient per 100 gallons. Such addition results in much improvedcontrol of harlequin bugs and stink bugs which often occur in cabbagealong with cabbage loopers.

EXAMPLE 3 Percent Methyl O-carbamylthiolacetohydroxamate 25.0Dimethylformamide 25.0 Methanol 50.0

dilution.

EXAMPLE 4 Percent Methyl O-carbamylthiolacetohydroxamate 25.0Dimethylformamide r 35.0 Methyl Cellosolve 40.0

The above water-soluble concentrate is prepared by stirring theingredients in a mixer. The concentrate is then used to treat cottonseed at a rate of 6 ounces of the active ingredient per '100 pounds ofseed. Seed treated in this way grow to produce seedlings which killcotton aphids (Aphis gossypz'i), which feed upon them up to 3 weeks ormore after planting. Cotton survival is improved if chloroneb is alsoapplied to the cotton seed along with the above concentrate at the rateof 6 ounces of active per 100 pounds of seed. And cotton survival isfurther improved, if as a third component of the treating preparation,Ceresan L is applied in an amount to provide 3 ounces of Ceresan L per100 pounds of cotton seed. The chloroneb in this mixture can be replacedby one or more of the following: pentachloro- 16 nitrobenzene; captan;tetramethylthiuram disulfide; l-chloro-2-nitropropane;S-ethoxy-3-trichloromethyl-1,2,4-thiadiazole; andp-dimethylaminobenzenediazo sodium sulfonate.

EXAMPLES 511 The following compounds are made in the manner of methylO-carbamylthiolacetohydroxamate of Example 1 by substituting anequivalent weight of the indicated starting material. The product isformulated and applied as in Example 1 to provide like results.

Starting material Product 5 Methyl acetohydroxamate. Methg lO-carbamylacetohydroxama e. 6 n-Butyl propionon-ButylO-carbamylproplonohydroxamate. hydroxamate. 7 n-Butylthiolproplonon-Butyl O-carbamylthlolhydroxamate. propionohydroxamate. 8Methyl thiolproplono- Methyl O-carbamylthiolhydroxamate.proplonohydroxamate. 9 Ethyl thiolaceto- Ethyl O-carbamylthiolacet0-hydroxarnate. hydroxamate. 10 Methyl thlolisobutyro- MethylO-carbamylthlollsohydroxamate. butyrohydroxamate. 11 Benzyl thiolaeeto-Benzyl O-earbamylthlolacetohydroxamate. hydroxamate.

EXAMPLE 12 To a stirred suspension of 48 parts of 50% sodium hydride inmineral oil and 1170 parts of tetrahydrofuran is added in portions 201.5parts of methyl p-chlorothiolbenzohydroxamate. The resulting sodium saltsuspended in tetrahydrofuran is added in portions to 297 parts ofphosgene in 1420 parts of ethyl ether maintained at 0-5 C. The excessphosgene is removed -by distillation at reduced pressure. The resultingmixture is added in portions to 34 parts of ammonia dissolved in 1050parts acetonitrile maintained at 0-l0 C. After warming to ambienttemperature the solids are filtered off and the filtrate is extractedwith hexane to remove mineral oil. The solvent is then removed yieldingmethyl O-carbamylp-chlorothiolbenzohydroxamate, which is recrystallizedfrom ethanol-water.

EXAMPLES 13-16 The following compounds are made in the manner of methylO-(canbamyl)-p-chlorothiolbenzohydroxamate of Example 12 by substitutingan equivalent weight of the indicated starting material.

Starting material Product 13 Methyl p-methylthlol- Methylp-methyl-O-carbamylbenzohydroxamate. thiolbenzohydroxamate. 14 Methylo-n-butoxythlo1- Methyl o n-butoxy-O-oarbamylbenzohydroxamate.thiolbenzohydroxamate. 15 Methyl p-bromothlol- MethylO-earbamyl-p-bromobenzohydroxamate. thiolbenzohydroxamate. 16 Methylp-chlorobenzo- Methyl O-carbamyl-p-chlorohydroxamate. benzohydroxamate.

EXAMPLE 17 Percent Methylp-chloro-O-(methylcarbamyl)thiolbenzohydroxamate 50.0 Dioctyl sodiumsulfosuccinate 1.5 Sodium lignin sulfonate 4.0 Methylated cellulose 1.0Fine silica 43.5

TABLE Continued Starting material Product 89 Methyl 4-bromo-2-methyl-Methyl O-(methylcarbamyD-4- thiolbenzohydroxamate.bromo-Z-methylthiolbenzohydroxamate.

90 Methyl lchlorol-nitro- Methyl O-(methylcarbamyD-2-thiolbenzohydroxamate. chlgroi-mtrothiolbenzohydroxama e.

91 Methyl 3-chloro-4-di- Methyl O-(methylcarbamyl)-3-methylaminothiolchloro-4-dimethylaminobenzohydroxamate.thiolbenzohydroxarnate.

92- Methyl 2-chloro-4-(tri- Methyl O-(methylearbamyl) -2- tluoromethyl)thiol chloro-4-triiluoromethylbenzohydroxamate. thiolbenzohydroxamate.

93 Methyl 3-bromothiolpro- Methyl O-(methylearbamyD-3- pionohydroxamate.hromothiolpropionohydroxamate.

94 Methyl carbobutoxythiol- Methyl O-(methylcarbamybacetohydroxamate.carbobutoxythiolacetohydroxamate.

95 Methyl 3-carbomethoxy- Methyl O-(methylcarbamyD-3-thiolpropionohydroxacarbomethoxythiolpropionomate. hydroxamate.

96 Methyl carbopentoxy- Methyl O(methylcarbamyl)-thiolformohydroxarnate. carhopentoxythiolformohydroxamate.

97 n-Hexyl thiolaceton-Hexyl O-(methylcarbamyD- hydroxamate.thiolacetohydroxamate.

98 Methyl 3 (methylthio)- Methyl O-(methylcarbamyD-3-thiolpropionohydroxa- (methylthio)thiolpropionomate. hydroxamate:

99. Propyl thiol-4-methyl- PropylOlmethylcarbamyhthiolvalerohydroxamate. 4-methylvalerohydroxamate.

100- Methyl methoxythiol- Methyl O-(methylcarbamyD- acetohydroxamate.methoxythiolacetohydroxamate.

101-...- Methyl o-methylthiol- MethylO-(methylcarbamyl)obenzohydroxamate. methylthiolbenzohydroxamate.

102. Methyl 4-tert.-butylthlol- Methyl O-(methylearbamyl)-4-benzohydroxamate. tert.-butylthiolbenzohydroxama e;

103...... Methyl 3-bromo-4-sec.- Methyl O-(methylcarbamyD-3-butylthiolbenzobromol-see.-butylthlbenzohydroxamate. hydroxamate.

104-....- Methyl 2-n-butoxy-3- MethylO-(methylearbamyl)-2-nm'trothiolbenzobutoxy3mtroth1olbenzohydroxamate.hydroxamate.

105"... Methyl Z-methoxythiol- Methyl O-(methylcarbamyl)-2-benzohydroxamate. methoxythiolbenzohydroxamate.

EXAMPLE 106 hydroxamate, is formulated and applied as follows:

'Percent Methyl O (dimethylcarbamyl)thiolacetohydroxamate 25.0 Sodiumlignosulfonate 2.0 Sodium alkylnaphthalenesulfonate 2.0 Dextrin 4.0Attapulgite 67.0

The ingredients are blended, coarsely ground through a hammer mill andthen passed through a fluid energy mill to produce particlessubstantially all below 10 microns.

The house fly (Musca domestica) is controlled in barns by using 1 poundof the above formula in 2.5 gallons of water and spraying the walls,floors, cracks, crevices, stalls and pens with a knapsack sprayer torun-off.

EXAMPLES 107-121 The following compounds are made in the manner ofmethyl O-(dimethylcarbamyl)thiolacetohydroxamate of Example 106 bysubstituting an equivalent weight of the indicated starting material forthe methyl thiolacetohydroxamate of Example 106. The product isformulated and applied in like manner to provide like results.

Starting material Product 107- Methyl thiolisobutyro- MethylO-(dimethylearbamyD- hydroxarnate. thiolisobutyrohydroxamate. 108 Methylp-ehlorothiol- Methyl O-(dimethylearbamyD- benzohydroxamate.p-chlorothiolbenzohydroxamate. 109 Ethyl thiolaceto- EthylO-(dimethylearbamyD- hydroxamate. thiolaeetohydroxamate. 110 Methyln-butyrohydroxa- Methyl O-(dimethylcarbamyD- mate. n-butyrohydroxamate.111 Methyl p-ehlorobenzo- Methyl O-(dimethylcarbamyD- hydroxamate.p-chlorobenzohydroxamate. 112 Methyl aeetohydroxamate. MethylO-(dimethylcarbamyD- aeetohydroxamate. 113 Benzyl aeetohydroxamate.Benzyl O-(dimethylcarbamyD- acetohydroxamate. 114 Methyl 2-(methylthlo)-Methyl O-(dimethylcarbamyl)- thiolacetohydroxamate.2-(methylthio)thiolaceto hydroxamate. 115 n-Butyl thiolaceton-ButylO-(dimethylcarbamyD- hydroxamate. thiolacetohydroxamate. 116 Methylpbromothiol- Methyl O-(dimethylearbamyD- benzohydroxamate.p-bromothiolbenzohydroxamate. 117 Isopropyl thiolaccto- IsopropylO-(dimethylcarbamyD- hydroxamate. thiolacetohydroxamate. 118 Isopropylthiolisobutyro- Isopropyl O-(dimethylearbamyD- hydroxarnate.thiolisobutyrohydroxamate. 119 Methyl 3 methoxythiol MethylO-(dimethylcarbamyl)- propionohydroxamate.3-methoxythiolpropionohydroxamate. 120 Ethyl thiolproplono- EthylO-(dimethylearbamyD- hydroxamate. thiolpropionohydroxamate. 121 Benzylthiolaceto- Benzyl O-(dimethylearbamyD- hydroxamate.thiolacetohydroxamate.

EXAMPLE 122 Preparation of methyl thiolacetimidate hydrochlorideintermediate A total of 41 parts of acetonitrile, 250 parts of anhydrousether and 48 parts of methyl mercaptan are stirred and maintained in anatmosphere of nitrogen as 36.5 Parts of dry HCl is gradually added tothe mixture. Near the end of the HCl addition the clear solution becomescloudy and a precipitate begins to form. The white crystals that formare collected by filtration, rinsed with cold ether, and dried in avacuum oven at room temperature. A total of 83 parts of hygroscopic,white, crystalline methyl thiolacetimidate hydrochloride is obtained,melting at 81-89 C.

Other imidate intermediates used in this invention can be made similarlywith corresponding alcohols, mercaptans and nitriles.

These imidates are reacted with hydroxylamine hydrochloride in thepresence of pyridine to give the corresponding reaction intermediatehydroxamates.

EXAMPLE 123 To a stirred solution of 105 parts of methylthiolacetohydroxamate in 400 parts of methylene chloride, at 25 C. isadded 60 parts of methyl isocyanate. The temperature rises duringaddition until the solvent begins to reflux. After the evolution of heatdiminishes the mixture is heated to reflux and stirred for an additional45 minutes. After removal of the solvent and drying, methyl 0-(methylcarbamyl)thiolacetohydroxamate is obtained as a white solid.

The product is then purified by recrystallization from water, and isformulated and applied as follows:

Percent Methyl O-(methylcarbamyl)thiolacetohydroxamate 97.5 Syntheticsilica 2.5

The above high-strength composition is prepared by coarse grinding theingredients and then passing them through a screen having 16 meshes/cm.On adding the concentrate to water at normal use ratio, the activeingredient dissolves.

Thus, the concentrated composition is added to water in an amount toprovide 0.75 lb. of active insecticide per 100 gallons of water. Alsoadded to the same water is a wettable powder formulation of1-(n-butylcarbamoyl)-2- benzimidazolecarboxylic acid, methyl ester, inan amount to furnish 0.75 pound of the active fungicide per 100 gallons.The water containing the compound of Formula 1 21 and the fungicide issprayed weekly on field rice at the rate of 100 gallons per acreproviding control of rice borers (Chilo spp.), and rice blast disease.

This mixture is blended and coarsely micropulverized.

This high-strength composition can be used in this form or furtherdiluted into other useful preparations, which may contain the abovecompound as the only active ingredient or may contain other pesticides.

The formulation as prepared here is added to water in an amount toprovide 0.4 pound of the active compound of this invention per 100gallons. Also added to this same water is an amount of a commercialmalathion formulation to provide 1.0 pound of malathion active per 100gallons. The water containing the two active ingredients is sprayed ontobacco in the field at IO-day intervals controlling tobacco budworms(Heliothis virescens), tobacco hornworms (Manduca sexta), andgrasshoppers. The malathion contributes largely to the control of thegrasshoppers. When other insects such as June beetles, suckflies orvegetable weevils are present the malathion can be replaced with TDE,DDT, Guthion," diazinon, parathion or carbaryl.

EXAMPLE 125 Percent Butyl O-(methylcarbamyl)thiolacetohydroxamate 75.0Sodium alkylnaphthalene sulfonate 2.0 Sodium ligninsulfonate 2.0 Dextrin4.0 Attapulgite 17.0

mate 35.0 Ethylene oxide condensate with nonylphenol 4.0 Calciumligninsulfonate 20 Synthetic fine silica 5.0 Kaolinite 54.0

While blending the dry ingredients, the liquid wetting agent is sprayedupon them. The blended composition is then passed through an impact milland finally reblended.

EXAMPLE 127 Percent Methyl p chloro O(methylcarbamyl)thiolbenzohydroxamate 25.00 Calcium ligninsulfonate 6.00Hydrated attapulgite 2.00 Monobasic potassium phosphate 1.00Phenylmercury acetate 0.25 Water 6 5.75

The solid ingredients are blended and micropulverized, mixed with thewater and the resulting slurry is sandground in conventional equipmentto produce particles substantially all below 2 microns. This formulationis diluted with water and applied to cotton infested with the 22 bollweevil Avzthonomus grandis by means of a tractormounted sprayer at therate of 0.5 to 2 pounds of active ingredient per acre. The infestationis elfectively controlled by this application.

EXAMPLE 128 Percent Methyl O- (methylcarbamyl) pbromothiolbenzohydroxamate 40.0 Polyoxyethylene sorbitol heptaoleate 8.0Synthetic fine silica 1.0 Parafiinic hydrocarbon oil 51.0

The slurry is sand-ground to produce particles substantially all below 5microns. The composition is emulsifiable in water.

This formulation is added to water in an amount to provide 0.25 pound ofactive ingredient per gallons. The resulting solution-suspension issprayed on apple trees on a weekly schedule providing control of greenpeach aphid (Myzus persicae), plum curculio (Conotrachelus neup'har),codling moth (Carpocapsa pomonella), and the red-banded leaf roller(Argyrotaenia velutz'nana).

Where more difiicult-to-control insects are present 01' where sprayingintervals are much longer, one or more of the following insecticides isadded to the spray in eifective amounts along with the compound of thisinvention: DDT, methoxychlor, malathion, parathion, lead arsenate,Guthion carbaryl or dieldrin.

EXAMPLE 12 9 Percent Methyl O-(methylcarbamyl) pchlorothiolbenzohydroxamate 3.0 Dichlorodifiuoromethane 57.0Trichlorofluoromethane 40.0

The solution is formed under pressure with moderate cooling and packedinto pressure vessels.

This aerosol formulation is applied in space application to a restaurantor other type of food establishment. House flies (Musca domestica),present at the time of application are killed.

The ingredients are combined and stirred with warming to produce ahomogeneous solution which can be diluted with water. This dilution ismade in a manner to provide 1.5 pounds of the active compounds of thisinvention in 10 gallons of Water. An emulsifiable formulation ofchlordane is also added in an amount to provide 1 pound active in 10gallons. The resulting composition is then sprayed on sugarcane seedpieces in the open furrow at the time of planting at the rate of 10gallons per 10,000 feet of row providing control of a variety ofinsects.

EXAMPLE 131 Percent Methyl O-(methylcarbamyl)thiolbutyrohydroxamate 20.0Methylene chloride 74.0 Blend of oil-soluble sulfonates andpolyoXyethylene ethers 6.0

The ingredients are combined and stirred to produce a homogeneousemulsifiable solution. This emulsifiable formulation is added to waterin an amount to provide 5 pounds of active ingredient per 100 gallons.Sprayed by air on field sugarcane foliage at the rate of 20 gallons (1.0pound active) per acre, at weekly intervals, this preparation providescontrol of armyworms and the sugarcane borer (Diazraea SLZGCIIQIEIZ'S).Where spray intervals are significantly longer than one week, one or 23more of the following insecticides is added to the spray in an effectiveamount: toxaphene, carbaryl, endrin or Guthion EXAMPLE 132 PercentMethyl O-(methylcarbamyl)thiolacetohydroxarnate 5.0 T rimethylnonylpolyethylene glycol ether 2.0 Phenylmercury acetate 0.1

Water 92.9

The ingredients are stirred to produce a solution.

This composition is diluted with water to a final concentration of 0.1%active. House flies (Musca domestica), and certain other flies such asstable flies (Stomoxys calcitrans), are controlled in farm buildings, inbarnyards and other outdoor locations by spraying this formulation as aspace spray by mist blower or directly to the flying or resting insectsby use of a hydraulic sprayer.

The formulation above, diluted to 10 pounds active ingredient per 100gallons is also applied at a rate of 100 gallons per acre to land beingrenovated for pasture, in order to control ticks.

EXAMPLE 13 3 Percent Methyl O- (methylcarbamyl)thiolacetohydroxamate36.1 Dimethylformamide 63.9

The above water-soluble concentrate which contains 3 pounds active pergallon is prepared by blending the components in a stirred vessel untilsolution of the active compound is complete. This preparation is sprayedby air as an ultra low volume (ULV) application on areas of deciduousforest at the rate of 0.3-0.5 gallon per acre providing control of thegypsy moth (Porthetria dispar). Where more resistant insects are alsopresent, one or more of the following insecticides are added ineffective amounts to the spray containing the compound of thisinvention: methoxychlor, DDT, carbaryl, malathion or toxaphene.

The above formulation is sprayed by air, without dilution, at the rateof 0.33 gallon per acre over forest areas containing fir, spruce, larch,hemlock and pine trees, for the control of the spruce budworm(Choristoneura fumiferma). The areas are sprayed when the larvae are inthe fourth and fifth instars. Nozzles and spray pressure are adjustedsuch that most of the droplets are approximately 5 microns in diameter.Excellent control of the budworm is obtained which results in good,sturdy shoot growth and a dark green, thrifty appearance. The tops oftrees in adjacent unsprayed areas appear as though scorched by fire, andmany of those trees heavily infested die.

In another area, a forest consisting primarily of balsam fir is sprayedwith a solution prepared by diluting one gallon of the above formulationwith 48 gallons of water. Application at the sub-lethal rate of onegallon of the dilute solution per acre is sufficient to knock the sprucebudworm larvae out of the trees and onto the ground below. Being unableto return to the trees, the larvae no longer impede the normal growth ofthe trees.

The above formulation is added to water in an amount to provide 0.75pound of active ingredient per 100 gallons. The water containing theinsecticide is then sprayed on field rice at l-day intervals providingcontrol of rice borers, Chilo spp.

Where insects such as the grape colaspis and stink bugs are present inaddition to rice borers, other insecticides such as EPN, carbaryl,Guthion, malathion. methyl parathion or parathion are also added to thespray.

EXAMPLE 134 Percent Methyl O-(-methylcarbamyl)acetohydroxamate 45Trimethylnonyl polyethylene glycol ether Cyclohexanone 50 Theingredients are combined and stirred to produce a homogeneous solution.This formulation is emulsified with water and applied in the mannerdescribed for the formulation of Example 131.

EXAMPLE 136 Percent Methyl p chloro-O- (methylcarbamyl)benzohydroxamate75 Sodium alkylnaphthalenesulfonate 2 Calcium ligninsulfonate 2Kaolinite clay 21 The ingredients are thoroughly blended andmicropulverized to produce particles substantially all below 50 microns.The composition may be used as a dust base or as a wettable powder.

EXAMPLE 137 Percent Methyl O-(methylcarbamyl)thiolacetohydroxamate 5.0Granular attapulgite (0.6-1.4 mm.) 95.0

The active component is warmed to 75 C. with three parts of water perpart of active and the resulting warm solution is sprayed on thegranules which are tumbled in a mixer. The granules are dried in acirculating air oven and then are ready for application.

Thhe granules prepared as described above are applied to the soil duringthe planting of corn, in the furrow, at a rate to provide 2.0 pounds ofactive ingredient per acre of field. This treatment gives control ofcorn rootworms and other soil insects. Where more difficult-to-kill soilinsect species are also present, granules containing one or more of thefollowing insecticides are added in effective amounts: parathion,aldrin, diazinon or phorate.

EXAMPLE 138 Percent Methyl O- (methylcarbamyl) thiolacetohydroxamate10.0 Granular attapulgite (0.40-0.85 mm.) 90.0

The active ingredient is dissolved in a minimum amount of methylenechloride and is then sprayed upon the attapulgite in a blender. Themethylene chloride is removed by air drying.

The granules prepared as described above are applied in the platingfurrows of potatoes at the rate of two pounds of active ingredient per10,000 linear feet of row. This treatment controls white-fringed beetlegrubs (Graphognathus leucoloma), in the soil and potato aphids(Macrosiphum euphorbiae), on the foilage for an extended period. Thisfoliage protection is due to the systemic movement of the compound ofthis invention from the soil up into the foliage. Where morediflicult-tokill insect species are also present in the soil, granulescontaining one or more of the following insecticides are added ineffective amounts: chlordane, DDT, diazinon or parathion.

EXAMPLE 139 Percent Methyl O- (methylcarbamyl) thiolacetohydroxamate 5.0

Granular attapulgite (0.6-1.4 mm.) 95.0

The finely divided active component is tumbled with the granules inorder to coat the surface. The entire mass is heated to 85 C. to meltthe active compound which is absorbed in and on the surface of thegranules. The cooled granules are then ready for application.

The granules prepared as described above are applied to small sweet cornplants at the rate of 20 pounds per acre. The application is made insuch a way that the granules roll down into the whorls of the plants.Corn earworms (Heliothis zea), attacking the growing area arecontrolled.

EXAMPLE 140 Percent MethylO-(methylcarbamyl)-p-chlorothiolbenzohydroxamate 20.0

Sodium sulfate 10.0

Calcium ligninsulfonates 13.0

Mississippi sub-bentonite 31.0

Kaolinite 26.0

This mixture is coarsely micropulverized and blended with about 18% byweight of water. This moist composition is extruded and cut to formpellets which are dried prior to use.

The pellets described here are used in the same manner as the granulesof Example 139 except that the use rate is pounds of pellets per acre.The insecticidal results of this application are the same as thoseobtained with the granules.

EXAMPLE 141 Equimolecular proportions ofmethyl-O-(rnethylcarbamyl)thiolacetohydroxamate and urea are dissolvedin excess methanol and the methanol is allowed to evaporate at roomtemperature. The residue melts sharply at 9697 C. either before or afterrecrystallization from methanol. Elemental analysis confirms a 1:1 molarcomplex of urea and methyl O-(methylcarbamyl)thiolacetohydroxamate.

Other complexes are prepared in like manner by substituting thiourea anddicyandiamide for urea to yield crystalline solids, M.P. ll2113 C. and113-115 C., respectively.

Methyl O-carbamyl thiolacetohydroxamate, as well as othercarbamylthiolacetohydroxamates, can be substituted for methylO-(methylcarbamyl)thiolacetohydroxamate with similar results.

EXAMPLE 142 Percent Methyl O (methylcarbarnyl) thiolacetohydroxamate1:1(complex with urea 95.0 Synthetic silica 5.0

The above composition is prepared by micropulverizing the ingredients toa particle size passing a 16 mesh/cm. screen.

The 1:1 complex of methyl O-carbamylthiolacetohydroxamate with urea canbe formulated in like manner.

The formulation of methyl O-carbamylthiolacetohydroxamate describedabove is added to water in an amount to provide 6 pounds of 1:1 complexper 100 gallons of water. This is sprayed on cotton plants at the rateof 25 gallons 1.5 pounds of complex) per acre providing control of bollweevil (Anthonomus grandis), and bollworms (Heliothis zea). Where moredifiicult-to-kill insect species are also present, an insecticidalamount of one or more of the following materials is added to the spray:DDT, endrin, carbaryl, malathion, methyl parathion, parathion, Guthion,or toxaphene.

26 EXAMPLE 143 Percent l,4-dichloro-2,S-dimethoxybenzene 50.0

Methyl O-(methylcarbamyl)thiolacetohydroxamate 25.0

Octylphenyl polyethylene glycol ether 1.0 Sodiumalkylnaphthalenesulfonate 0.75 Sodium lignin sulfonate 2.75 Syntheticsilica 0.75 Diatomaceous earth 2.75 Thiuram 10.0 Magnesium carbonate 7.0

The above components are blended and micropu1verized to pass a 24 mesh/cm. screen. This wettable powder can be applied by spraying or in a seedtreater to coat seeds.

The above formulation is applied to cotton seed in a standard seedtreater at the rate of 12 ounces of formulation per pounds of cottonseed along with 3 ounces of Ceresan L per 100 pounds of seed. Suchtreatment prevents seed and seedling loss due to Pythium and Rhizoctoniaas well as seedling damage by aphids and certain other insects. Whereother soil fungi such as Fusarium are considered to be a hazard,1-(n-butylcarbamoyl)- Z-benzimidazolecarbamic acid, methyl ester, isalso added to the seed at the same rate as the1,4-dichloro-2,5-dimethoxybenzene.

EXAMPLE 144 Percent Methyl O-(methylcarbamyl)thiolacetohydroxamate 50.0Ethylmercury p-toluenesulfonanilide 2.0 Thiuram 25.0 Synthetic silica3.0 Attapulgite clay 16.5 Sodium alkylnaphthalene sulfonate 1.0 Calciumlignin sulfonate 2.5

The above components are blended and micropulverized to a particle sizeessentially below 50 microns. This wettable powder can be suspended inwater and used to treat seeds or with appropriate dilution, as a spray.

The above formulation is added to cotton seed in a standard slurry seedtreater at the rate of 16 ounces of formulation per 100 pounds of seed.This treatment protects the seed from attack by soil fungi, and insects.It also protects the seedling from attack by cotton aphids (A phisgossypii), for an extended period by systemic movement of the methylO-(methylcarbamyl)thiolacetohydroxamate from the area of the seed upinto the seedling.

EXAMPLE 145 Percent Methyl O- (methylcarbamyl)thiolacetohydroxamate 10.0

Ethylmercury p-toluenesulfonanilide 7.0 Thiuram 25.0 Synthetic silica3.0 Attapulgite clay 51.5 Sodium alkylnaphthalene sulfonate 1.0 Calciumlignin sulfonate 2.5

EXAMPLE 146 Percent Methyl O-(methylcarbamyl) thiolacetohydroxamate 50.0Ethylmercury p-toluenesulfonanilide 0.1 Thiuram 25.0 Synthetic silica3.0 Attapulgite clay 18.4 Sodium alkylnaphthalene sulfonate 1.0

Calcium lignin sulfonate 2.5

The above components are blended and micropulverized to a particle sizeessentially below 50 microns. This wettable powder can be suspended inwater and used to treat seeds or, with appropriate dilution, as a spray.

The above formulation is added to cotton seed in a standard slurry seedtreater at the rate of 15 ounces of formulation per 100 pounds of seed.This treatment protects the seed from attack by soil fungi and insects.It also protects the seedling from attack by cotton aphids (Aphz'sgossypii), for an extended period by systemic movement of the methylO-(methylcarbamyl)thiolacetohydroxamate from the area of the seed upinto the seedling.

EXAMPLE 147 Percent Methyl O (methylcarbamyl)thiolacetohydroxa mate 50.0

l-(n-butylcarbamoyl) 2 benzimidazolecarboxylic acid, methyl ester 25.0Kaolinite clay 20.0 Sodium dihydrogen phosphate 1.0 Sodiumalkylnaphthalene sulfonate 2.0 Calcium lignin sulfonate 2.0

The above components are blended and micropulverized to a particle sizeessentially below 25 microns. This wettable powder is suitable for usein spraying fruit trees and vegetable crops.

This formulation is added to water at the rate of 1.0 pound offormulation per 100 gallons of water. When the resulting preparation issprayed on apple trees on a regular schedule at the rate of 300 gallonsper acre, the trees are protected from attack by insects such as aphids,codling moth (Carpocapsa pomonella), and plum curculio (Conotrachelusnenuphar), as well as from diseases including apple scab and powderymildew.

The following formulation is prepared in the manner described above, andwhen used in a similar manner, gives similar results.

Percent Methyl O-(methylcarbamyl)thiolacetohydroxamate 50 OL-(2,4dichlorophenyl)-u-phenyl-5-pyrimidinemeth- Maneb 40.0 Methylatedcellulose 2.0 Sodium alkylnaphthalenesulfonate 1.0 Kaolinite 16.0

The above ingredients are blended and micronized to a particle sizepassing a screen having 0.25 millimeter square openings. This wettablepowder when suspended in water is suitable for spraying vegetable crops.

The formulation described above is added to water at the rate of 3.0pounds per 100 gallons. When this liquid is sprayed on tomato plants ona weekly schedule, the plants are protected from attack by insects andsuch diseases as bacterial spot and late blight.

EXAMPLE 149 Percent 1,4-dichloro-2,5-dimethoxybenzene 20.0 Methyl O(methylcarbamyl)thiolacetohydroxamate 10.0 Trimethylnonyl polyethyleneglycol ether 5.0 Methylene chloride 65.0

EXAMPLE 150 Percent Methyl O (methylcarbamyl)thiolacetohydroxamate 20.0Methylmercury 2,3-dihydroxypropyl mercaptide 0.5 Methylmercury acetate0.1 Methanol 50.0

Water 29.4

The above solution is prepared by mixing the components. It can be useddirectly for seed treatment and also can be diluted with water andsprayed. When this formulation is applied to cotton seed at the rate of30 ounces per pounds, the seed is protected from fungus decay in thesoil and the seedlings that develop resist attack by aphids and otherinsects due to the systemic movement of the compound of this invention.

EXAMPLE 151 Percent Methyl O (methylcarbamyl)thiolacetohydroxamate 23.0EPN 23.0 Dimethylformamide 49.0 Blend of polyoxyethylene ethers ofoil-soluble sulfonates 5.0

The above components are mixed to form a homogeneous solution which canbe applied directly, as in ULV application, or which forms a sprayablesuspension when added to water, xylene, or non-phytotoxic spray oils.Methyl O-carbamylthiolacetohydroxamate can be formulated and applied inlike manner. The above formulation is added to water at the rate of 2.0pounds per 100 gallons. When the resulting suspension is sprayed onpotato plants at the rate of 100 gallons per acre on a regular weeklyschedule, the plants are protected from attack by a wide variety ofinsects.

EXAMPLE 152 Percent Methyl O-carba'mylthiolacetohydroxamate 15.0 DDT30.0 Dimethylformamide 50.0

Blend of polyoxyethylene ethers of oil-soluble sulfonates 5 .0

The above components aremixed to form a homogeneous solution which canbe applied directly, as in ULV application, or which when added to waterforms a sprayable suspension. The solution can also be diluted withnon-phytotoxic spray oils, or low-boiling aromatic hydrocarbons.

When this formulation is diluted with water and sprayed on corn plantsat the rate of 2.0 pounds of formulation per acre, the corn plants areprotected from attack by a wide variety of foliage insects.

Methyl O-(methylcarbamyl)thiolacetohydroxamate can be formulated andused in like manner.

EXAMPLE 153 Percent Methyl O-carbamylthiolacetohydroxamate 10.0Toxaphene 40.0 Dimethylformamide 45.0

Blend of polyoxyethylene ethers of oil-soluble sulfonates The abovecomponents are mixed and warmed to form a homogeneous solution which canbe sprayed as a ULV application or which forms a sprayable suspensionwhen added to water, non-phytotoxic spray oils, or low-boiling aromatichydrocarbons.

Strobane can be substituted for toxaphene and dimethylacetamide fordimethylformamide with similar results. These formulations are useful inprotecting a wide variety of plants from a number of damaging insects.

EXAMPLE 154 Percent Methyl O-carbamylthiolacetohydroxamate 95.0Synthetic silica 5.0

The above high-strength composition is prepared by coarse grinding andscreening through a screen having 0.42 millimeter square Openings.

This composition is stirred into water in an amount to provide 0.5 poundof the active ingredient per 100 gallons. The resulting solution isapplied as a wetting spray to cabbage plants on which cabbage loopers(Trichoplusia ni), are feeding. Good control of the cabbage loopers isobtained.

EXAMPLE 1 5 6 Methyl 'O-(methylcarbamyl)-p-nitrothiolbenzohydroxamate isincorporated in a synthetic laboratory diet for boll weevils at a rateof 0.0002 percent by weight (2 parts per million). Weevils feeding onthis diet lay eggs but none of these eggs hatch. Similar weevils feedingon the same diet without the methyl O-(methylcarbamyl)-p-nitrothiolbenzohydroxamate lay eggs that hatch to produce normalliving young.

EXAMPLE 157 Percent 1,2-dibromo-3-chloropropane 60 MethylO-(methylcarbamyl)thiolacetohydroxamate 12 Blend of alkylarylpolyetheralcohols with organic sulfonates 8 Alkylnaphthalene (principally amethylnaphthalene) 20 These ingredients are combined with simple mixingto form a homogeneous liquid.

This emulsifiable liquid is dispersed in water at a rate that provides36 pounds of the active ingredients per 100 gallons of water. Theresulting dilute emulsion is sprayed over the root zone of rose bushesat a rate of 100 gallons per acre. The area is then irrigated with aquantity of water sufiicient to carry the active ingredient into theroot zone of the rose bushes. Excellent control is obtained of daggernematodes (Xiphinema spp.), allowing the treated bushes to grow in anormal manner. In addition, the bushes are protected from aphids andother insects. Similarly, infested rose bushes which are not treatedgrow poorly and produce flowers having little ornamental value.

EXAMPLE 158 Percent Methyl O methylcarbamoyl)thiolacetohydroxa- Theabove ingredients are stirred with warming until a homogeneous solutionis obtained. The resulting emulsifiable concentrate is added to water inan amount to give 65 grams of active ingredient per liters of spray.This emulsion is sprayed on apple trees to the point of run-01f by meansof a high pressure hydraulic sprayer. Sprays on a weekly scheduleprovide control of green apple aphid (Aphis pomi), codling moth(Carpocapsa pomo nella), plum curculio (Conotrachelus nenup-har), andred-banded leaf roller (Argyrotaenia velutinana). One or more of thefollowing insecticides in effective amounts can be added to the spraywhen a longer interval between applications is desired or it is neededto control other especially difficult-to-control pests: methoxychlor,malathion or carbaryl.

EXAMPLE 159 Percent Powder of Example 2 21.5 Activated charcoal 78.5

The above ingredients are blended and ground through a hammer-nil] to aparticle size essentially less than 50 microns. The product is furtherdiluted by blending with tale to obtain a dust containing 2% methylO-carbamylthiolacetohydroxamate. The resulting formulation is dustedonto cabbage on a weekly schedule at a rate of 20 pounds per acre.Excellent control of insects, attacking cabbage, including the cabbagelooper (Trichoplusia ni), and the imported cabbage worm (Pieris rapae)is obtained.

EXAMPLE 160 Percent Methyl O- (methylcarbamyl thiolacetohydroxamate 38.05,6-dihydro-2-methyl-p-oxathiin-3-carboxanilide 37.0 Octyl phenylpolyethylene glycol ether 1.0 Sodium alkyl naphthalene sulfonate 0.75Sodium lignin sulfonate 2.75 Synthetic silica 0.75 Diatomaceous earth2.75 Thiuram 10.0 Magnesium carbonate 7.0

The above components are blended and micropulverized to pass a 24mesh/cm. screen. The resulting wettable powder can be applied byspraying or in a seed treater to coat seeds.

The above formulation is applied to wheat seed in a standard seedtreater at the rate of 12 ounces of formulation per 100 pounds of wheatalong with 1 ounce of Ceresan L. When plated the treated seed germinatesand grows well protected from damage by the greenbug (Schizaphisgraminum), as well as from fungi including loose and covered smut.

EXAMPLE 1 61 Percent Bran 98 MethylO-(methylcarbamyl)thiolacetohydroxamate 2 The bran is tumbled while a20% acetone solution of methyl 0 (methylcarbamyl)thiolacetohydroxamateis sprayed over the surface. After thorough mixing the contents of thetumbler are discharged into a shallow pan and air dried.

Just prior to use the bait is moistened with one-half its weight ofwater and then broadcast over an area planted to truck crops with aspreader at the rate of 2 kg./ha. It is spread evenly over both thefoliage and soil, and gives excellent control of garden slugs. The baitis reapplied on an as-needed basis to control this pest. As a beneficialside effect, the bait also controls grasshoppers, cutworms, army-worms,crickets and earwigs.

The dry bait described above is moistened with half its weight of watercontaining 2% black strap molasses. It is spread evenly in a band overtobacco plants at the rate of 1 kg. per 8,900 meters of row on a 7-dayschedule 31 starting at the first signs of serious pest infestation.Good control of both the tobacco budworm and hornworm is obtained.

EXAMPLE 162 Percent Dry dog food meal 99 MethylO-(methylcarbamyl)thiolacetomethoxamate l The dry dog food meal istumbled while a 20% solution of the active ingredient dissolved inacetone is sprayed over the surface. After thorough mixing, the bait ispoured into shallow pans and air dried. It may be packaged for use assuch. Alternatively, sufficient water is added to plasticize the massand it is extruded through a 3 cm. die, chopped into sections and dried.These pellets are placed singly into especially made cans which haveholes out along the bottom edge to allow the insects to feed. Cans areplaced out of reach of children and pets in areas infested withcockroaches. Excellent control of these pests is obtained.

Combinations of methyl O-(methylcarbamyl)thiolacetohydroxamate withS-methyl 1-(dimethylcarbamoyl)- N [(methylcarbamoyl)oxy]thioformimidateare especially useful for controlling both insects and nematodes. Thecombinations can be used in the ratios of 1:10 to 10:1 with 1:3 to 3:1being preferred. They can be made either prior to formulation or aftereach has been formulated separately. The combinations can be formulatedin as many different ways as are described for the separate activeingredients. Use rates vary with the crop being protected, weatherconditions, and the specific pests controlled, but generally are from 2to 12 pounds per acre when used in the furrow at planting time, and from/2 to 1 /2 pounds per 100 gallons per acre when used as a foliar spray.

EXAMPLE 163 Percent Methyl O-(methylcarbamyl)thiolacetohydroxamate 5 Smethyl 1 (dimethylcarbamoyl)-N-[(methylcarbamoyl)oxy] thioformimidate 5Dimethylformamide M.P78 Celatom granules 80 The two active ingredientsand the dimethylformamide are stirred into solution, and then sprayedover the Celatom granules which are being tumbled in a rotary blendor.Care is taken to assure good distribution of the active ingredients ontothe granules. The granule absorbs the dimethylformamide making itunnecessary to dry them. They are then packaged for use.

The above formulation is applied at the rate of 6 pounds active per acrein a 18-inch band to a field of tobacco just prior to transplantingtime. The band is rotovated lightly to a depth of 4 inches and the youngtobacco plants are set out. The field is known to be infested withseveral species of nematodes such as Meliodogne incognita,Tylenchorhynchus spp., Pratylenchus spp., Paratylenchus, spp., andXiphinema spp. The tobacco plants treated in this fashion are observedto grow well free from the depredations of both the nematodes, and earlyseason insects such as flea beetles. Conventional insecticide sprays maybe applied late in the season for additional control of tobacco budwormand/ or hornworm, if desired.

EXAMPLE 164 One hundred parts of the dimethylformamide solution ofExample 163 is diluted further with 100 parts of dimethylformamide toprovide a liquid formulation containing 2 pounds of active ingredientper gallon.

Three pints of this formulation (commodity basis) are diluted with 100gallons of water and used to spray an acre of tobacco plants. Theseplants are sprayed in a similar fashion from shortly after transplantingto two weeks before harvest on a 6-7 day schedule. Execllent control ofthe following insects is obtained: flea beetles, hornworms, budworms andcabbage loopers. In addition, the

32 plants are larger and more vigorous than similar but untreated plantsbecause of the nematode control which is provided by this combination.

EXAMPLE 165 Percent Methyl O-(methylcarbamyl)thiolacetohydroxamate 7S-methyl 1-(dimethylcarbamoy1)-N-[(methylcarbamoy1)oxy]thioformimidate18 Dimethylformamide 75 The above-listed ingredients are stirredtogether to form a solution with a total active ingredient content of 2pounds per gallon.

One quart of this solution is extended with gallons of water and sprayedover an acre of potatoes repeatedly on a 5-7 day schedule throughout thegrowing season. Excellent control of such insects as flea beetles,Colorado potato beetle, potato tuber worm and aphids is observedresulting in a higher yield of potato tubers than obtained from anadjacent but untreated acre plot. The tubers are also higher in qualitydue to the much lower incidence of attack by the root knot nematode,Meliodogyne incognita.

The invention claimed is:

1. An insecticidal composition comprising an agricultural adjuvant andan insecticidally effective amount of a compound of the formula:

wherein R is naphthyl; or

wherein X is hydrogen, fluorine, chlorine, bromine, di-

methylamino, nitro, cyano, or trifluoromethyl;

Y is hydrogen, chlorine, alkyl or 1 through 4 carbon atoms, or alkoxy of1 through 4 carbon atoms;

Z is hydrogen, or chlorine, with the limitation that Z is chlorine onlywhen both X and Y are chlorine;

R is hydrogen or methyl;

R is hydrogen or methyl;

R is alkyl of 1 through 6 carbon atoms, benzyl, or

chlorobenzyl; and

Q is sulfur.

2. The composition of claim 1 in which the compound is methyl p-chloro O(methylcabamyl)thiolbenzohydroxamate.

3. A method for controlling insects comprising applying to a locus to beprotected an insecticidally effective amount of a compound of theformula:

wherein R is naphthyl; or I wherein X is hydrogen, fluorine, chlorine,bromine, di-

methylamrno, nitro, cyano, or trifluoromethyl;

33 Y is hydrogen, chlorine, alkyl of 1 through 4 carbon atoms, or alkoxyof 1 through 4 carbon atoms; Z is hydrogen, or chlorine, with thelimitation that Z is chlorine only when both X and Y are chlorme; R ishydrogen or methyl; R is hydrogen or methyl; SR, is alkyl of 1 through 6carbon atoms, benzyl or chlorobenzyl; and Q is sulfur. 4. The methodaccording to claim 3 wherein the compound is methylpchloro-O-(methylcarbamyDthiolbenzohydroxamate.

References Cited UNITED STATES PATENTS ALBERT T. MEYERS, PrimaryExaminer L. SCHENKMAN, Assistant Examiner US. Cl. X.R.

